The present invention relates to photochemical singlet oxygen generators having a cationic axial substituent which enhances the substantivity of said singlet oxygen generators for fabric surfaces. The photochemical singlet oxygen generators described herein are useful in laundry detergent compositions as bleaching agents. The present invention also relates to methods for bleaching fabrics with the photochemical singlet oxygen generators.
It is known that certain water soluble phthalocyanine, naphthalocyanine, mixed cyanine and metallocyanine compounds can be used as photobleaching and anti-microbial agents. Phthalocyanines, naphthalocyanine, mixed cyanine and metallocyanines can form xe2x80x9csinglet oxygenxe2x80x9d.
Singlet oxygen can be formed by chemical as well as photochemical processes. Singlet oxygen is a highly oxidative species capable of reacting with substances, for example, with stains on a fabric to bleach them to a colorless and usually water-soluble state. There are many examples of phthalocyanines and naphthalocyanines photobleaches, the most common being the zinc and aluminum phthalocyanines. In the literature the term xe2x80x9cphotosensitizerxe2x80x9d is often used instead of xe2x80x9cphotoactivatorxe2x80x9d and may therefore be considered as standing equally well for the latter term used throughout this specification.
The prior art teaches phthalocyanine and naphthalocyanine compounds having the general structure 
where Me is a transition or non-transition metal (Sens.) is a phthalocyanine or naphthalocyanine ring which, when combined with a suitable Me unit, is capable of undergoing photosensitization of oxygen molecules, R units are substituent groups which are bonded to the photosensitization ring units (Sens.) to enhance the solubility or photochemical properties of the molecule, and Y units are substituents associated with the metal atom, for example, anions to provide electronic neutrality.
It has been a task of formulators of photobleaches to modify the properties of the (Sens.) unit of the molecule to increase the quantum efficiency without reducing the water solubility. Typically this has been accomplished by substitution on the photochemical (Sens.) ring. However, substitution on the macrocyclic ring is frequently difficult and can adversely affect other photobleach properties such as color, substantivity and photoefficiency.
Surprisingly, it has been found that the compounds of the present invention allow formulators to increase the photoefficiency of the singlet oxygen generators without adversely affecting the other parameters of the molecule. In addition, the substantivity of the photochemical singlet oxygen generator for fabric surface can be modified without producing an undesired effect in the photophysics of the molecule. This ability to delineate and selectively modify these key structural elements contributing to the target properties of the molecule allows the formulator to proceed without having to rely upon a xe2x80x9chit and missxe2x80x9d stratagem.
The present invention provides a means by which an effective photosensitizer can be made to have an enhanced affinity for the surface of fabric, especially cotton fabric. This task is achieved by attaching an axial cationic moiety to the singlet oxygen generator. This axial cationic moiety is capable of interacting with various surfaces, especially fabric surfaces which can contain a negative charge. By this interaction, the cationic group draws the photoactive singlet oxygen producing portion of the molecule into proximity with the surface of the fabric where the bleaching action of the photosensitizer can take place on stains.
It is therefore an object of the present invention to provide photochemical singlet oxygen generators which serve as photobleaches and which have a higher efficiency for cleaning stains on fabric. It is a further object of the present invention to provide photobleaching compositions suitable for use as laundry detergent bleaching compositions.
It is a yet further object of the present invention to provide enhanced photobleaching hard surface cleaning compositions for non-porous hard surfaces, inter alia, Formica(copyright), ceramic tile, glass, or for porous hard surfaces such as concrete or wood.
It is a still further object of the present invention is to provide a method for bleaching fabric with laundry compositions comprising the photobleaching compounds of the present invention.
It is yet still a further object of the present invention is to provide a method for cleaning hard surfaces with the photobleaching compounds of the present invention.
Various patent documents relate, to photochemical bleaching or to the use of cyanine compounds as well as their formulation and synthesis. See for example U.S. Pat. No. 3,094,536 issued Jun. 18, 1963; U.S. Pat. No. 3,927,967 issued Dec. 23, 1975; U.S. Pat. No. 4,033,718 issued Jul. 5, 1977; U.S. Pat. No. 4,166,718 issued Sep. 4, 1979; U.S. Pat. No. 4,240,920 issued Dec. 23, 1980; U.S. Pat. No. 4,255,273 issued Mar. 10, 1981; U.S. Pat. No. 4,256,597 issued Mar. 17, 1981; U.S. Pat. No. 4,318,883 issued Mar. 9, 1982; U.S. Pat. No. 4,368,053 issued Jan. 11, 1983; U.S. Pat. No. 4,497,741 issued Feb. 5, 1985; U.S. Pat. No. 4,648,992 issued Mar. 10, 1987; and U.K. Pat. App. 1,372,035 published Oct. 30, 1974; U.K Pat. App. 1,408,144 published Oct. 1, 1975; U.K. Pat App. 2,159,516 published Dec. 4, 1985; E.P. 285,965 A2; E.P. 381,211 A2 published Aug. 8, 1990; E.P. 484,027 A1 published May 6, 1992; WO 91/18006 published Nov. 28, 1991 and Japanese Kokai 06-73397 Derwent Abst. No. (94-128933) published Mar. 15, 1994.
In addition to the above cited patent publications, other references describing the synthesis, preparation and properties of cyanines, incorporated herein also by reference; Phthalocyanines: Properties and Applications, Leznoff, C. C. and Lever A. B. P. (Eds), VCH, 1989; infrared Absorbing Dyes, Matsuoka, M. (Ed), Plenum, 1990; Inorg. Chem., Lowery, M. J. et at., 4, pg. 128, (1965); Inorg. Chem. Joyner R. D. et al., 1, pg. 236, (1962); Inorg. Chem., Kroenke, W. E. et al., 3, 696, 1964; Inorg. Chem. Esposito, J. N. et al., 5, pg.1979, (1966); J. Am. Chem. Soc. Wheeler, B. L. et al., 106, pg. 7404, (1984); Inorg. Chem. Ford, W. E, et al., 31, pg. 3371, (1992); Material Science, Witkiewicz, Z. et al., 11, pg. 39, (1978); J. Chem. Soc. Perkin Trans. I, Cook, M. J., et al., pg. 2453, (1988); J. Chin Chem. Soc., 40, pg. 141, (1993); J. Inorg. Nucl. Chem., 28, pg. 899, (1966); Polymer Preps, 25, pg. 234, (1986); Chem. Lett., 2137, (1990); J. Med. Chem., 37, pg. 415, (1994).
The present invention relates to singlet oxygen generators useful as a bleaching agent in laundry detergent compositions, said singlet oxygen generators having the formula: 
wherein P is a photosensitizer unit; R is an axial moiety which mediates the solubility of the singlet oxygen generator; and D is a unit which increases the fabric substantivity of the singlet oxygen generator, said unit having the formula:
xe2x80x83xe2x80x94L1xe2x80x94E or xe2x80x94L1xe2x80x94Bxe2x80x94[L2xe2x80x94E]m
wherein E is a unit which comprises a tetravalent nitrogen having the formula: 
wherein each R30-R35 is linear and branched C1-C22 alkyl, linear and branched C1-C22 alkenyl, substituted and unsubstituted aryl, substituted and unsubstituted alkylenearyl, substituted and unsubstituted aryloxy, substituted and unsubstituted alkyleneoxyaryl, substituted and unsubstituted oxyalkylenearyl, alkyleneoxyalkyl, or any R30-R35 can be taken together to form a nitrogen-containing ring, and mixtures thereof; X is a water soluble anion; B is a branching unit having the formula: 
wherein B is selected from the group consisting of boron, aluminum, nitrogen, phosphorous, carbon, silicon, tin, germanium, and mixtures thereof, preferably carbon or silicon; and L1 and L2 are linking units, provided said linking units when taken together with said B unit comprise a total of at least 2 continuous covalent bonds from said P unit to said E units; m is from 2 to 4.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The present invention relates to photochemical singlet oxygen generators which have an enhanced substantivity for fabric surfaces. This increase in fabric substantivity is due to the cationic nature of the axial D units which are substituted on the photosensitizer unit.
The present invention also relates to cleaning compositions which comprise the photochemical singlet oxygen generators of the present invention. Laundry detergent compositions according to the present invention comprise:
a) at least about 0.1%, preferably from about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to about 20% by weight, of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof;
b) at least about 0.001 ppm, preferably from about 0.01 to about 10000 ppm, more preferably from about 0.1 to about 5000 ppm, most preferably form about 10 to about 1000 ppm, of a singlet oxygen generator having the 
wherein P is a photosensitizer unit; R is an axial moiety which mediates the solubility or substantivity of the singlet oxygen generator; and D is a unit which increases the fabric substantivity of the singlet oxygen generator, said unit having the formula
xe2x80x94L1xe2x80x94E or xe2x80x94L1xe2x80x94Bxe2x80x94[L2xe2x80x94E]m
wherein E is a unit which comprises a tetravalent nitrogen having the formula: 
wherein each R30-R35 is linear and branched C1-C22 alkyl, linear and branched C1-C22 alkenyl, substituted and unsubstituted aryl, substituted and unsubstituted alkylenearyl, substituted and unsubstituted aryloxy, substituted and unsubstituted alkyleneoxyaryl, substituted and unsubstituted oxyalkylenearyl, alkyleneoxyalkyl, or any R30-R35 can be taken together to form a nitrogen-containing ring, and mixtures thereof; X is a water soluble anion; B is a branching unit having the formula: 
wherein B is selected from the group consisting of boron, aluminum, nitrogen, phosphorous, carbon, silicon, tin, germanium, and mixtures thereof, preferably carbon or silicon; and L1 and L2 are linking units, provided said linking units when taken together with said B unit comprise a total of at least 2 continuous covalent bonds from said P unit to said E units; m is from 2 to 4; and
c) the balance carriers and adjunct ingredients, said adjunct ingredients are selected from the group consisting of buffers, builders, chelants, filler salts, soil release agents, dispersants, enzymes, enzyme boosters, perfumes, thickeners, abrasives, solvents, clays, and mixtures thereof.
Photosensitizing Units, P
The photosensitizers of the present invention suitable for use as photobleaches and photodisinfectants comprise cyanine rings as well as hybrid cyanine rings. The cyanine rings are those formed from four identical aromatic units, for example, phthalocyanines and naphthalocyanines. The hybrid rings are formed by chemically reacting together at least two different aromatic monomer units capable of forming a hybrid cyanine ring. Typically, cyanine rings are defined by the type of aromatic monomer unit used to synthesize the target macrocyclic ring, for example, phthalocyanines are formed from derivatives of benzene, naphthalocyanines are formed from derivatives of naphthalene, etc.
The cyanine rings of the present invention have the general formula 
wherein A, B, C, and D represent aromatic rings. For the purposes of the present invention these aromatic rings are preferably substituted or unsubstituted benzene, 1,2-naphthalene, 2,3-naphthalene, anthracene, and phenanthrene. However, this list is not meant to be inclusive or exclusive of any other aromatic ring capable of insertion into the cyanine ring including aromatic heterocyclic rings inter alia quinolines or isoquinolines.
For the purpose of further illustrating the formation of hybrid cyanine rings useful for preparing the singlet oxygen generators of present invention, the scheme below depicts the expected mixture of cyanine rings obtained when the cyanine ring forming monomers, 1,6-dimethoxy-3,4-dicyanobenzene and 1,6-dibromo-3,4-dicyanobenzene, are reacted together under suitable conditions. 
Reacted together under suitable conditions yield: 
Other examples include but are not limited to the reaction of orthodicyanobenzene and 2,3-dicyanonaphthalene as shown below 
or the reaction of the corresponding phthalimidines as shown below 
to yield the mixture of hybrid cyanines I-VI shown below. 
For the purposes of the present invention ring components derived from substituted and unsubstituted benzene can be written in either of two equivalent resonance formulas: 
wherein R1, R2, R3 and R4 are each independently selected from the substituents described herein below.
For the purposes of the present invention ring components derived from substituted and unsubstituted 2,3-naphthylene can be written in either of two equivalent resonance formulas: 
wherein R1, R2, R3, R4, R5, and R6 are independently selected from the substituents described herein below.
For the purposes of the present invention ring components derived from substituted and unsubstituted 1,2-naphthylene can be written in either of two equivalent resonance formulas: 
wherein R1, R2, R3, R4, R5, and R6 units are independently selected from the substituents listed herein below.
For the purposes of the present invention ring components derived from substituted and unsubstituted anthracene can be written in either of two equivalent resonance formulas: 
wherein R1, R2, R3, R4, R5, R6, R7, and R8 units are independently selected from the substituents described herein below.
For the purposes of the present invention ring components derived from substituted and unsubstituted phenanthrene can be written in either of two equivalent resonance formulas: 
wherein R1, R2, R3, R4, R5, R6, R7, and R8 units are independently selected from the substituents described herein below.
Each R1, R2, R3, R4, R5, R6, R7, and R8 unit is independently:
a) hydrogen;
b) halogen;
c) hydroxyl;
d) C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl;
e) halogen substituted C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl;
f) polyhydroxyl substituted C3-C22 alkyl;
g) C1-C22 alkoxy, preferably C1-C4 alkoxy, more preferred methoxy;
h) branched alkoxy having the formula 
wherein Z is hydrogen, hydroxyl, C1-C30 linear alkyl, C1-C30 branched alkyl, C1-C30 alkoxy, xe2x80x94CO2H, xe2x80x94OCH2CO2H, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, xe2x80x94PO32xe2x88x92M, xe2x80x94OPO32xe2x88x92M, and mixtures thereof; M is a water soluble cation in sufficient amount to satisfy charge balance; x is 0 or 1, each y independently has the value from 0 to 6, preferably from 0 to 6; each z independently has the value from 0 to 100, preferably from 0 to about 10, more preferably from 0 to about 3;
i) substituted aryl, and unsubstituted aryl having essentially the formula: 
wherein R13 and R14 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C3-C6 alkenyl, C1-C6 alkoxy, C3-C6 branched alkoxy, halogen, xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, xe2x80x94N(R15)2, and xe2x80x94N+(R15)3Xxe2x88x92 wherein each R15 is independently hydrogen or C1-C4 alkyl; and mixtures thereof; preferably hydrogen C1-C6 alkyl, xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, and mixtures thereof, more preferably R13 or R14 is hydrogen and the other moiety is C1-C6 alkyl; wherein M is a water soluble cation and X is a water soluble anion;
j) substituted alkylenearyl and unsubstituted alkylenearyl having essentially the formula: 
wherein R13 and R14 are as defined above, p is from 1 to about 10.
k) substituted aryloxy and unsubstituted aryloxy having essentially the formula: 
wherein R13 and R14 are as defined above.
l) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl units are defined as moieties having essentially the formula: 
wherein R13 and R14 are as defined above, q is from 0 to about 10.
m) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl having essentially the formula: 
wherein R13 and R14 are as defined above, w is from about 1 to about 10.
n) C1-C22 linear thioalkyl, C3-C22 branched thioalkyl, C1-C22 linear substituted thioalkyl, C3-C22 branched substituted thioalkyl, and mixtures thereof;
o) ester units of the formula xe2x80x94CO2R9 wherein R9 is C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, all of which can be substituted with halogen; poly-hydroxyl substituted C3-C22 alkyl, C3-C22 glycol; C1-C22 alkoxy, C3-C22 branched alkoxy; substituted and unsubstituted aryl, alkylenearyl, aryloxy, oxyalkylenearyl, alkyleneoxyaryl; preferably C1-C22 alkyl, C3-C22 branched alkyl, and mixtures thereof;
p) alkyleneamino units having essentially the formula: 
wherein R10, and R11 are each a C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, R12 is hydrogen, C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl and mixtures thereof, the index v is 0 or 1; A is xe2x80x94Oxe2x80x94 of xe2x80x94NHxe2x80x94; X is a water soluble anion, u is from 0 to 22, preferably u is from 3 to about 10, provided that if v is 1 then u is greater than or equal to 1. Examples of water soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species include chloride, bromide, sulfate, hydrogen sulfate, phosphate and the like;
q) an amino unit of the formula
xe2x80x94NR17R18
wherein R17 and R18 are each a C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, or mixtures thereof;
r) alkylethyleneoxy units having essentially the formula:
xe2x80x94(A)vxe2x80x94(CH2)y(OCH2CH2)xZ
wherein Z is hydrogen, hydroxyl, xe2x80x94CO2H, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, C1-C6 alkoxy, substituted and unsubstituted aryl, substituted and unsubstituted aryloxy; alkyleneamino as defined herein above; or mixtures thereof; A units comprise nitrogen or oxygen, preferably oxygen; M is a water soluble cation; v is 0 or 1; x is from 0 to 100, preferably from 0 to 20, more preferably from 0 to 5; y is from 0 to 12, preferably from 1 to 4; however, no peroxide xe2x80x94Oxe2x80x94Oxe2x80x94 bonds are contained within the photobleaching compounds of the present invention;
s) siloxy and substituted siloxy of the formula xe2x80x94OSiR19R20R21 wherein each R19, R20, and R21 is independently selected from the group consisting of C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, or mixtures thereof, substituted or unsubstituted aryl, aryloxy; alkylethyleneoxy units of the formula:
xe2x80x94(A)vxe2x80x94(CH2)y(OCH2CH2)xZ
wherein Z is hydrogen, hydroxyl, C1-C30 alkyl, xe2x80x94CO2H, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, C1-C6 alkoxy; substituted or unsubstituted aryl, and aryloxy; alkyleneamino as defined herein above, and mixtures thereof, preferably hydrogen or C1-C6 alkyl, more preferably methyl; v is 0 or 1; x is from 1 to 100, preferably from 0 to about 20, more preferably from 3 to about 10; and y is from 0 to 12, preferably from about 0 to about 5.
Cationic Substantivity Units, D
The photochemical singlet oxygen generators of the present invention comprise one or more xe2x80x9ccationic substantivityxe2x80x9d units. For the purposes of the present invention xe2x80x9ccationic substantivityxe2x80x9d units are defined as xe2x80x9cunits which serve to increase the ability of the photochemical singlet oxygen generator to approach the fabric surface wherein the production of singlet oxygen molecules serve to chemically modify dirt, stains, and soil to a water soluble formxe2x80x9d. Cationic Substantivity Units, have the formula: 
wherein P is a photosensitizer unit; R is an axial moiety which mediates the solubility of the singlet oxygen generator; and D is a unit which increases the substantivity of the singlet oxygen generator for fabric surfaces, said unit having the formula
xe2x80x94L1xe2x80x94E or xe2x80x94L1xe2x80x94Bxe2x80x94[L2xe2x80x94E]m
wherein E is a unit which comprises a tetravalent nitrogen having the formula: 
wherein each R30-R35 is linear and branched C1-C22 alkyl, linear and branched C1-C22 alkenyl, substituted and unsubstituted aryl, substituted and unsubstituted alkylenearyl, substituted and unsubstituted aryloxy, substituted and unsubstituted alkyleneoxyaryl, substituted and unsubstituted oxyalkylenearyl, as described herein above; or any R30-R35 can be taken together to form a nitrogen-containing ring.
Preferably R30-R35 is an alkyleneoxyalkyl having the formula: 
wherein R16 is hydrogen of C1-C4 alkyl; Z is C1-C18 alkyl, C1-C20 alkoxy, substituted or unsubstituted aryl, xe2x80x94CO2M, xe2x80x94OCH2CO2M, xe2x80x94SO3M, and mixtures thereof; M is a water soluble cation; the index x has the value from 1 to 6, the index y has the value from 1 to 30.
X is a water soluble anion which provides charge balance for the cationic substantivity unit. X can be any water soluble unit which is compatible with the balance of the photosensitizing molecules. If more than one cationic group is present, that is more than one positive charge is present due to cationic moieties, an X unit having a negative charge equal to the number of positive charges is therefore suitable for use. For example, two positive charges may be suitably neutralized by the presence of a sulfate (SO42xe2x88x92) unit. Non-limiting examples or X units are the water soluble anions such as chlorine (Clxe2x88x92), bromine (Brxe2x88x92) and iodine (Ixe2x88x92) or X can be any negatively charged radical such as sulfate (SO42xe2x88x92), methosulfate (CH3SO3xe2x88x92), etc.
B is a branching unit having the formula: 
wherein B is selected from the group consisting of boron, aluminum, nitrogen, phosphorous, carbon, silicon, tin, germanium. and mixtures thereof, preferably carbon or silicon; and L1 and L2 are linking units; m is from 2 to 4.
Preferred L1 and L2 units are independently selected from the group consisting of oxygen, linear or branched alkylene, linear or branched alkenylene; linear or branched alkyleneoxy, substituted or unsubstituted arylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted aryleneoxy, substituted or unsubstituted oxyalkylenearylene, substituted or unsubstituted alkyleneoxyarylene, and mixtures thereof, defined herein further below.
For the purposes of the present invention an oxygen molecule may serve as a suitable L1 unit, preferably when directly bonded to a branching unit to form a moiety having the general formula: 
For the purposes of the present invention linear or branched alkylene moieties are defined as units having the formula: 
wherein R16 is C1-C4 alkyl; the index i has the value from 1 to 30, the index j has the value from 1 to 30. If only one linking group L1 is present between the photosensitizer unit P and the harvester unit E then the value of i+j must be at least 20.
For the purposes of the present invention linear or branched alkenylene moieties are defined as moieties comprising one or more units, or combinations of units having the formula: 
wherein R16 is C1-C4 alkyl; the index i has the value from 1 to 30. In the case where only one linking group L1 is present between the photosensitizer unit P and the harvester unit E then the values of i and j must be sufficient to provide at least 20 covalent bonds between said photosensitizer unit P and said harvester unit E.
For the purposes of the present invention linear or branched alkyleneoxy moieties which comprise the L1 or L2 units described herein below, are defined as units or a combination of units having the formula: 
wherein R16 is C1-C4 alkyl; the index x has the value from 2 to 4; whereas the values of the indices i, j and k must have sufficient value for at least 20 covalent bonds between the photosensitizer unit P and the harvester unit E.
For the purposes of the present invention substituted or unsubstituted arylene moieties are defined as 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene units having essentially the formula: 
wherein R16 is hydrogen, C1-C4 alkyl, and mixtures thereof. Arylene units may be used alone or in combination with other suitable moieties to form L1 and L2 units.
For the purposes of the present invention substituted or unsubstituted alkylenearylene moieties are defined as 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene units having essentially the formula: 
wherein R16 is hydrogen, C1-C4 alkyl, and mixtures thereof alkylenearylene units may be used alone or in combination with other suitable moieties to form L1 and L2 units.
For the purposes of the present invention substituted and unsubstituted aryleneoxy moieties are defined as 1,2-phenyleneoxy, 1,3-phenyleneoxy, and 1,4-phenyleneoxy units having essentially the formula: 
wherein R16 is hydrogen, C1-C4 alkyl, and mixtures thereof. Aryleneoxy units may be used alone or in combination with other suitable moieties to form L1 and L2 units.
For the purposes of the present invention substituted and unsubstituted oxyalkylenearylene moieties are defined as 1,2-oxyalkylenephenylene, 1,3-oxyalkylenephenylene, and 1,4-oxyalkylenephenylene units having essentially the formula: 
wherein R16 is hydrogen, C1-C4 alkyl, and mixtures thereof, the index w has the value from 1 to 30. Oxyalkylenarylene units may be used alone or in combination with other suitable moieties to form L1 and L2 units.
For the purposes of the present invention substituted and unsubstituted alkyleneoxyarylene moieties are defined as 1,2-alkyleneoxyphenylene, 1,3-alkyleneoxyphenylene, and 1,4-alkyleneoxyphenylene units having essentially the formula: 
wherein R16 is hydrogen, C1-C4 alkyl, and mixtures thereof, the index q has the value from 1 to 30. Alkyleneoxyarylene units may be used alone or in combination with other suitable moieties to form L1 and L2 units.
The D units of the present invention also optionally comprise branching units B said units essentially having the formula: 
wherein B is selected from the group consisting of boron, aluminum, nitrogen, phosphorous, carbon, silicon, tin, germanium, and mixtures thereof, preferably carbon or silicon, more preferably carbon.
The following formulas are examples of suitable cationic moieties having enhanced fabric substantivity properties: 
wherein these axial moieties may be combined with any suitable anionic Xxe2x88x92 unit.
Substantivity and Solubility Mediating Axial R Units
The singlet oxygen generators of the present invention optionally comprise an R unit. Substantivity and solubility mediating axial R units, are bonded directly to the photoactive metal or non-metal atom which is chelated by the photosensitizing unit and occupies a position axial to the essentially planar photosensitizing unit. The utility of each R unit is primarily directed to the solubility or substantivity properties of the compounds of the present invention. The selection of an R unit can be made, in addition to, or in lieu of, solubility requirements, and be totally directed instead to the xe2x80x9csubstantivityxe2x80x9d or xe2x80x9cnon-substantivityxe2x80x9d of the compound. R units are essentially nonionic, cationic, or anionic units.
For the purposes of the present invention the term xe2x80x9csubstantivityxe2x80x9d is defined as xe2x80x9cthe ability for a molecule to bind, adhere, or have a general affinity for a surfacexe2x80x9d inter alia fabric and hard surfaces.
The axial R units suitable for use as substantivity or solubility mediation units of the present invention include:
a) hydrogen;
b) halogen;
c) hydroxyl;
d) C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl;
e) halogen substituted C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl;
f) polyhydroxyl substituted C3-C22 alkyl;
g) C1-C22 alkoxy, preferably C1-C4 alkoxy, more preferred methoxy;
h) branched alkoxy having the formula 
wherein Z is hydrogen, hydroxyl, C1-C30 linear alkyl, C1-C30 branched alkyl, C1-C30 alkoxy; xe2x80x94CO2H, xe2x80x94OCH2CO2H, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, xe2x80x94PO32xe2x88x92M, xe2x80x94OPO32xe2x88x92M, and mixtures thereof; M is a water soluble cation in sufficient amount to satisfy charge balance; x is 0 or 1, each y independently has the value from 0 to 6, preferably from 0 to 6; each z independently has the value from 0 to 100, preferably from 0 to about 10, more preferably from 0 to about 3.
i) substituted aryl, and unsubstituted aryl having essentially the formula: 
wherein R13 and R14 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C3-C6 alkenyl, C1-C6 alkoxy, C3-C6 branched alkoxy, halogen, xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x80x94M+, xe2x80x94N(R15)2, and xe2x80x94N+(R15)3Xxe2x88x92 wherein each R15 is independently hydrogen or C1-C4 alkyl; and mixtures thereof; preferably hydrogen C1-C6 alkyl, xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, and mixtures thereof, more preferably R13 or R14 is hydrogen and the other moiety is C1-C6 alkyl; wherein M is a water soluble cation and X is a water soluble anion.
j) substituted alkylenearyl and unsubstituted alkylenearyl having essentially the formula: 
wherein R13 and R14 are as defined above, p is from 1 to about 10.
k) substituted aryloxy and unsubstituted aryloxy having essentially the formula: 
wherein R13 and R14 are as defined above.
l) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl units are defined as moieties having essentially the formula: 
wherein R13 and R14 are as defined above, q is from 0 to about 10.
m) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl having essentially the formula: 
wherein R13 and R14 are as defined above, w is from about 1 to about 10.
n) C1-C22 linear, C3-C22 branched thioalkyl, C1-C22 linear, C3-C22 branched substituted thioalkyl, and mixtures thereof;
o) carboxylate units of the formula 
wherein R9 is C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, all of which can be substituted with halogen;
poly-hydroxyl substituted C3-C22 alkyl, C3-C22 glycol; C1-C22 alkoxy, C3-C22 branched alkoxy; substituted and unsubstituted aryl, alkylenearyl, aryloxy, oxyalkylenearyl, alkyleneoxyaryl; preferably C1-C22 alkyl, C314 C22 branched alkyl, and mixtures thereof;
p) alkyleneamino units having essentially the formula: 
wherein R10, and R11 are each a C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, R12 is hydrogen, C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl and mixtures thereof, the index v is 0 or 1; X is a other water soluble anion, u is from 0 to 22, preferably u is from 3 to about 10. Examples of water soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species include chloride, bromide, sulfate, hydrogen sulfate, phosphate and the like;
q) an amino unit of the formula
xe2x80x94NR17R18
wherein R17 and R18 are each a C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, or mixtures thereof;
r) alkylethyleneoxy units having essentially the formula:
xe2x80x94(A)vxe2x80x94(CH2)y(OCH2CH2)xZ
wherein Z is hydrogen, hydroxyl, xe2x80x94CO2H, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+, C1-C6 alkoxy, substituted and unsubstituted aryl, substituted and unsubstituted aryloxy; alkyleneamino as defined herein above; or mixtures thereof; A units comprise nitrogen or oxygen, preferably oxygen; M is a water soluble cation; v is 0 or 1; x is from 0 to 100, preferably from 0 to 20, more preferably from 0 to 5; y is from 0 to 12, preferably from 1 to 4; however, no peroxide xe2x80x94Oxe2x80x94Oxe2x80x94 bonds are contained within the photobleaching compounds of the present invention;
s) siloxy and substituted siloxy of the formula xe2x80x94OSiR19R20R21 wherein each R19, R20, and R21 is independently selected from the group consisting of C1-C22 alkyl, C3-C22 branched alkyl, C2-C22 alkenyl, C3-C22 branched alkenyl, or mixtures thereof, substituted or unsubstituted aryl, aryloxy; alkylethyleneoxy units of the formula:
xe2x80x94(A)vxe2x80x94(CH2)yxe2x80x94(OCH2CH2)xZ
wherein Z is hydrogen, hydroxyl, C1-C30 alkyl, xe2x80x94CO2H, xe2x80x94SO3xe2x88x92M+, OSO3xe2x88x92M+, C1xe2x80x94C6 alkoxy; substituted or unsubstituted aryl, and aryloxy; alkyleneamino as defined herein above, and mixtures thereof, preferably hydrogen or C1-C6 alkyl, more preferably methyl; v is 0 or 1; x is from 1 to 100, preferably from 0 to about 20, more preferably from 3 to about 10; and y is from 0 to 12, preferably from about 0 to about 5.
According to the present invention the preferred axial R units comprise moieties having the formula
xe2x80x94Yixe2x80x94Kj and xe2x80x94Yixe2x80x94Qj
wherein Y is a linking moiety selected from the group consisting of O, CR25R26, OSiR25R26, OSnR25R26, and mixtures thereof; wherein R25 and R26 are hydrogen, C1-C4 alkyl, halogen, and mixtures thereof; i is 0 or 1, j is from 1 to 3;
K is a ligand selected from the group consisting of:
a) C1-C30 linear alkyl, C3-C30 branched alkyl, C2-C30 linear alkenyl, C3-C30 branched alkenyl, C6-C20 aryl, C7-C20 arylalkyl, C7-C20 alkylaryl, and mixtures thereof;
b) an alkylethyleneoxy unit of the formula
xe2x80x94(R23)y(OR22)xOZ
wherein Z is selected from the group consisting of hydrogen, C1-C20 alkyl, C3-C20 branched alkyl, C2-C20 linear alkenyl, C3-C20 branched alkenyl, C6-C20 aryl, C7-C30 arylalkyl, C6-C20 alkylaryl, and mixtures thereof; R22 is selected from the group consisting of C1-C4 linear alkylene, C3-C4 branched alkylene, C3-C6 hydroxyalkylene, and mixtures thereof; R23 is selected from the group consisting of C2-C20 alkylene, C3-C20 branched alkylene, C6-C20 arylene, C7-C30 arylalkylene, C7-C30 alkylarylene, and mixtures thereof; x is from 1 to 100; y is 0 or 1; and
Q is an ionic moiety having the formula:
xe2x80x83xe2x80x94R24xe2x80x94W
wherein R24 is selected from the group consisting of C3-C30 linear alkylene, C3-C30 branched alkylene, C2-C30 linear alkenylene, C3-C30 branched alkenylene, C6-C16 arylene, and mixtures: thereof; W is selected from the group consisting of xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94SO3xe2x88x92M+; PO32xe2x88x92M+, xe2x80x94OPO3xe2x88x92M+, xe2x80x94N+(R27)3Xxe2x88x92; wherein R27 is independently. hydrogen, C1-C6 alkyl, xe2x80x94(CH2)nOH, xe2x80x94(CH2CH2O)nH, and mixtures thereof; wherein n is from 1 to 4; M is a water soluble cation of sufficient charge to provide electronic neutrality and X is a water soluble anion as defined herein above.
Preferred axial R units are alkyl alkyleneoxy units of the formula
xe2x80x94(R23)y(OR22)xOZ
wherein Z is selected from the group consisting of hydrogen, C7-C20 linear alkyl, C3-C20 branched alkyl, C2-C20 linear alkenyl, C3-C20 branched alkenyl, C6-C10 aryl, C7-C20 arylalkyl, C7-C20 alkylaryl, and mixtures thereof; R22 is selected from the group consisting of C1-C4 linear alkylene, C3-C4 branched alkylene, and mixtures thereof; R23 is selected from the group consisting of C2-C6 alkylene, C3-C6 branched alkylene, C6-C10 arylene, and mixtures thereof; x is from 1 to 50; y is 0 or 1.
More preferred axial R units; comprise y equal to 0, Z is hydrogen, C1-C20 alkyl, C3-C20 branched alkyl, C6-C10 aryl, and mixtures thereof, most preferred Z is hydrogen or C6-C20 linear alkyl, C10-C20 branched alkyl; R22 is C1-C4 linear or C3-C4 branched alkylene.
Also preferred R units having the formula:
xe2x80x94Yixe2x80x94Qj
wherein Y is a linking moiety selected from the group consisting of O, CR25R26 OSiR25R26, OSnR25R26, and mixtures thereof; i is 0 or 1, j is from 1 to 3; Q is an ionic moiety having the formula:
xe2x80x94R24xe2x80x94W
wherein R24 is selected from the group consisting of C2-C20 linear alkylene, C3-C20 branched alkylene, C2-C20 linear alkenylene, C3-C20 branched alkenylene, C6-C10 arylene, and mixtures thereof; W is selected from the group consisting of xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+; PO32xe2x88x92M+, xe2x80x94OPO3xe2x88x92M+, xe2x80x94N+(R27)3Xxe2x88x92; where independently hydrogen, C1-C6 alkyl, (CH2)nOH, xe2x80x94(CH2CH2O)nH, and mixtures thereof; wherein n is from 1 to 4; M is a water soluble cation of sufficient charge to provide electronic neutrality and X is a water soluble anion as defined herein above.
A preferred hydrophilic R has the index i equal to 1; R24 is C3-C20 linear alkylene, C3-C20 branched alkylene, W is xe2x80x94CO2xe2x88x92M+, xe2x80x94SO3xe2x88x92M+, xe2x80x94OSO3xe2x88x92M+; M is a water soluble cation of sufficient charge to provide electronic neutrality.
Examples of Y units suitable, for use in R units having the formula:
xe2x80x94Yixe2x80x94Kj
have the formula
xe2x80x94Oxe2x80x94K1, xe2x80x94Snxe2x80x94K1, xe2x80x94OSnxe2x80x94K1
wherein i is equal to 1 and j is equal to 1. Further examples have the formula 
wherein i is equal to 1 and j is equal to 3. The above examples also apply to Y units when used with Q ionic moieties.
An example of a preferred photochemical singlet oxygen generator according to the present invention has the following formula: 
wherein the photosensitizer unit P comprises an unsubstituted silicon(IV) phthalocyanine (R1-R4 of each benzene ring is hydrogen) and there are two identical D cationic units wherein L1 is an alkyleneoxy unit having the formula: 
wherein the indices j and k are equal to 0, x is equal to 2, and i is equal to 1, and the E is has the formula wherein R30 and R31 are each hydroxyethyl and R32 is methyl, Xxe2x88x92 is any suitable water soluble anion.
Further examples of photochemical singlet oxygen generators according to the present invention are the silicon(IV) phthalocyanines having the general formula: 
wherein for the first example each D, unit has the formula: 
wherein L1 is and alkyleneoxy unit wherein the indices j and k are each equal to 0; x is equal to 2 and i is equal to 2; B is a silicon atom providing three branching points; a first pair of L2 units which are alkyleneoxy units wherein the indices j and k are each equal to 0; x is equal to 17, and i is equal to 1 wherein each L2 unit is connected to an E moiety wherein each R30-R32 are methyl; the remaining L2 unit is an alkyleneoxy unit wherein j and k are each equal to 0; x is equal to 6, and i is equal to 1 wherein the L2 moiety connects an E unit wherein R30 and R31 are each hydroxyethyl and R32 is methyl; Xxe2x88x92 is any suitable water soluble anion.
The present invention also relates to laundry detergent compositions comprising:
a) at least about 0.001% by weight, of a detersive surfactant, said detersive surfactant selected from the group consisting of anionic, cationic, zwitterionic, nonionic, and ampholytic surfactants, and mixtures thereof;
b) at least about 0.001 ppm, preferably from about 0.01 to about 10000 ppm, more preferably from about 0.1 to about 5000 ppm, most preferably form about 10 to about 1000 ppm, of a source of singlet oxygen having the formula 
wherein P is a photosensitizing group; each D is independently a moiety which is capable of enhancing the production of singlet oxygen; and R is an axial moiety which mediates the solubility or substantivity of the singlet oxygen generator as described herein above; and
c) the balance carriers and adjunct ingredients.
Preferably the laundry detergent compositions of the present invention comprise from about 0.1% to about 30% by weight, preferably from about 1% to about 30% by weight, more preferably from about 5% to about 20% by weight, of detersive surfactant.
The laundry detergent compositions of the present invention may be liquid, granular or semi-solid, for example a gel, paste, or viscous cream.
The present invention also relates to a method for cleaning a stained fabric comprising contacting a stained fabric in need of cleaning with an aqueous cleaning solution comprising at least 0.001% of the singlet oxygen generator according to the present invention followed by exposing the surface of the treated fabric to a source of light having a minimal wavelength range from about 300 to about 1200 nanometers.
Surfactantxe2x80x94The instant singlet oxygen generator containing compositions comprise from about 0.001% to about 60% by weight of a surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surface active agents. For liquid systems, surfactant is preferably present to the extent of from about 0.1% to 20% by weight of the composition, For solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems, surfactant is preferably present to the extent of from about 1.5% to 30% by weight of the composition.
Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight, include the conventional C11-C18 alkyl benzene sulfonates (xe2x80x9cLASxe2x80x9d) and primary, branched-chain and random C10-C20 alkyl sulfates (xe2x80x9cASxe2x80x9d), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3xe2x88x92M+)CH3 and CH3(CH2)y(CHOSO3xe2x88x92M+)CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates (xe2x80x9cAExSxe2x80x9d; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates (xe2x80x9cAExe2x80x9d) including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines (xe2x80x9csultainesxe2x80x9d), C10-C18 amine oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are described further herein and are listed in standard texts.
Anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids are derived from coconut oil sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
Additionally, secondary alkyl sulfates may be used by the formulator exclusively or in conjunction with other surfactant materials and the following identifies and illustrates the differences between sulfated surfactants and otherwise conventional alkyl sulfate surfactants. Non-limiting examples of such ingredients are as follows.
Conventional primary alkyl sulfates, such as those illustrated above, have the general formula ROSO3xe2x88x92M+ wherein R is typically a linear C8-22 hydrocarbyl group and M is a water solublizing cation. Branched chain primary alkyl sulfate surfactants (i.e., branched-chain xe2x80x9cPASxe2x80x9d) having 8-20 carbon atoms are also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed Jan. 21, 1991.
Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl xe2x80x9cbackbonexe2x80x9d of the molecule. Such materials may be depicted by the structure
CH3(CH2)n(CHOSO3xe2x88x92M+)(CH2)mCH3
wherein m and n are integers of 2 of greater and the sum of m+n is typically about 9 to 17, and M is a water-solublizing cation.
The aforementioned secondary alkyl sulfates are those prepared by the addition of H2SO4 to olefins. A typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued Feb. 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued Dec. 24, 1991. The synthesis conducted in solvents which afford the secondary (2,3) alkyl sulfates on cooling, yields products which, when purified to remove the unreacted materials, randomly sulfated materials, unsulfated by-products such as C10 and higher alcohols, secondary olefin sulfonates, and the like, are typically 90+% pure mixtures of 2- and 3-sulfated materials (some sodium sulfate may be present) and are white, non tacky, apparently crystalline, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5% of the mixture of secondary (2,3) alkyl mono-sulfates. Such materials are available as under the name xe2x80x9cDANxe2x80x9d, e.g., xe2x80x9cDAN 200xe2x80x9d from Shell Oil Company.